CN110993365A - Self-growing bimetallic MOF on foamed nickel and derivative electrode material thereof - Google Patents
Self-growing bimetallic MOF on foamed nickel and derivative electrode material thereof Download PDFInfo
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- CN110993365A CN110993365A CN201911153485.7A CN201911153485A CN110993365A CN 110993365 A CN110993365 A CN 110993365A CN 201911153485 A CN201911153485 A CN 201911153485A CN 110993365 A CN110993365 A CN 110993365A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
The invention discloses a self-growing bimetal MOF on foamed nickel and a derivative electrode material thereof, which takes a bimetal MOFs sheet as a precursor to grow an array-shaped porous NiCo on a foamed nickel substrate2S4Nanosheets. The method does not need a conductive agent and a binder, and forms the layered porous NiCo by utilizing the controllable growth of the CoNi-MOF and the preparation process of annealing before vulcanizing2S4The structure can promote the rapid transmission of electrons, reduce the charge transfer resistance and be beneficial to maintaining the stability and the better cycle performance of the structure, and tests show that the NiCo prepared by the method2S4The array nanosheet has ultrahigh specific capacity, the specific capacity can reach 1354.4F/g under the current density of 1A/g, and the capacity can be kept at 82.6% after the current density of 8A/g is circulated for 10000 circles.
Description
Technical Field
The invention belongs to the technical field of nano materials and energy raw materials, and particularly relates to an electrode material for self-growing bimetallic MOF (metal organic framework) on foamed nickel and derivatives thereof.
Background
With the rapid development of the times and the leapfrog progress of science and technology, the demand of human beings on energy sources is larger and larger, and the awareness of environmental protection is also gradually enhanced, so that new energy sources and green and environment-friendly energy storage modes become increasingly concerned topics of people. The super capacitor is a very ideal green portable energy storage mode, and has high power density, specific capacitance and good cycle stability. The performance of the supercapacitor is closely related to electrode materials, and at present, the supercapacitor can be used as a plurality of electrode materials, including carbon materials, transition metal oxides, high polymer, composite materials and the like, wherein the carbon materials have good cycle stability but small specific capacity, and the transition metal oxides have poor cycle stability but ultrahigh specific capacity, so that how to improve the cycle stability of the supercapacitor by overcoming the structural change of the materials in the charging and discharging process on the premise of keeping high energy density and high power density becomes an important problem to be solved urgently at present.
Metal Organic Frameworks (MOFs) are important materials in the fields of catalysis, energy conversion, energy storage and the like due to their controllable porosity, large specific surface area, diverse structures and functions and the like. However, due to inherent defects of low electronic conductivity, poor reversible redox reaction and the like of the MOFs, the application of the MOFs in the field of energy storage is limited. The electrochemical performance of the single metal MOFs derivatives is often difficult to meet the current requirements for good electrode materials. Other metal ions are introduced into the structure of the MOFs derivative to synthesize various metal compounds, so that the method is an effective way for improving the electrochemical performance of the MOFs derivative. In this case, the synergy between the different metal ions significantly improves the overall electrochemical performance. For example, Guan's group developed a hollow NiCo obtained by nickel ion etching Co-MOF2O4Nanoplatelets for use in supercapacitors and electrocatalysis. Zhang synthesizes a double-shell Co (OH)2the/LDH nano material is used as a sulfur carrier of a lithium battery. Despite the progress made to date, few unbonded electrode derivatives extracted directly from bimetallic MOFs have been reported. Therefore, it remains a challenge to directly implement reasonable bimetallic MOFs derivatives as unbonded electrodes for energy storage.
Disclosure of Invention
Aiming at the problems of poor cycling stability of transition metal materials and the like, the invention aims to provide an electrode material for self-growing bimetallic MOF and derivatives thereof on foamed nickel.
In order to achieve the above purpose, the invention adopts the following technical scheme.
A self-growing bimetallic MOF on foamed nickel and a preparation method thereof comprise the following steps:
step 1: slowly adding a 2, 6-naphthalenedicarboxylic acid dimethyl salt solution into a mixed solution of cobalt acetate and nickel acetate;
step 2: and (3) transferring the clean foamed nickel into the solution obtained in the step (1), and standing for a period of time at the temperature of 25-80 ℃ to obtain the self-growing bimetallic MOF (NF/CoNi-MOF) on the foamed nickel.
Preferably, the mass ratio of the cobalt acetate to the nickel acetate to the dimethyl 2, 6-naphthalenedicarboxylate is 1-2: 1: 2.
Preferably, the size of the foamed nickel is 1cmx1cm, and the clean foamed nickel is obtained by ultrasonic cleaning with acetone, deionized water, hydrochloric acid and ethanol in sequence.
Preferably, the mixture is placed at 25-80 ℃ for 10-48 h.
Self-growing bimetallic MOF derivative electrode material namely arrayed NiCo on foamed nickel2S4The preparation method of the nanosheet comprises the following steps:
step a: annealing the self-grown bimetallic MOF on the foamed nickel;
step b: carrying out hydrothermal reaction on the annealed foam nickel and sodium sulfide solution at the temperature of 90-120 ℃ for a period of time, washing and drying to obtain the electrode material, namely the arrayed NiCo2S4Nanosheets.
As an improvement, in the step a, the annealing temperature is 350 +/-10 ℃, and the annealing time is 2 hours.
As an improvement, in the step b, the concentration of the sodium sulfide solution is 0.2-0.4 mol/L.
As an improvement, in the step b, the hydrothermal reaction is carried out for 12-24h at 90-120 ℃.
Compared with the prior art, the invention has the advantages that:
(1) provides a method for preparing porous NiCo on a foamed nickel matrix by using a novel bimetallic MOFs sheet as a precursor2S4A method of nanoplatelet array. The method mainly comprises the controllable growth of bimetallic CoNi-MOF and the preparation process of annealing before vulcanizing. The layered porous unbonded electrode has the advantages of fast electrolyte diffusion, high-activity active sites, stable structure, low charge transfer resistance and ultrahigh specific capacity.
(2) The defects of poor conductivity and poor reversibility of reduction-oxidation reaction of the MOFs are overcome by vulcanizing the annealed MOFs, and the specific capacity of the electrode material is greatly increased.
(3) The method has the advantages of simple preparation process, low equipment requirement and process technical requirement, and low cost.
Drawings
FIG. 1 is a diagram of self-growing bimetallic MOF and arrayed NiCo on foamed nickel in accordance with the present invention2S4The preparation method is shown in the process flow chart.
FIG. 2 is an SEM image of the self-grown bimetallic MOF on foamed nickel at different reaction times (a and b are SEM topography maps of 10h reaction time, c and d are SEM topography maps of 20h reaction time, and e and f are SEM topography maps of 48h reaction time) according to the invention.
FIG. 3 is an array of derivatives of NiCo of the present invention2S4SEM image of nanoplatelets.
FIG. 4 is an array of derivatives of NiCo of the present invention2S4TEM images of the nanoplates.
FIG. 5 is a schematic representation of an arrayed NiCo of the present invention2S4Multiplying power maps of the nanosheets under different current densities in a three-electrode test.
FIG. 6 is a schematic representation of an arrayed NiCo of the present invention2S4The nanosheets are assembled into an electrochemical performance map in a hybrid supercapacitor test (a is a multiplying power performance test map of the hybrid supercapacitor, and b is a cycle performance map of the hybrid supercapacitor after 10000 cycles under the current density of 4A g-1 and an LED lamp lighted by the cycle performance map).
Detailed Description
The present invention is further illustrated by the following examples and figures, but the content of the present invention is not limited to these examples.
With reference to fig. 1, the process of making self-growing bimetallic MOF and its derivatives electrode materials on foamed nickel in accordance with the present invention is embodied by examples 1-5.
Example 1:
the method comprises the following steps: 40mg of nickel acetate and 80mg of cobalt acetate were dissolved in 30ml of deionized water, 80mg of 2, 6-naphthalenedicarboxylic acid dipotassium salt was dissolved in 30ml of water, and the solution was added dropwise to form a uniform solution, followed by stirring for 5 minutes.
Step two: and (3) placing 4 pieces of 1cm x1cm foamed nickel (sequentially washed and ultrasonically by acetone, deionized water, hydrochloric acid and ethanol) into the mixed solution in the step one, and transferring the mixed solution into a 60 ℃ oven to react for 20 hours to obtain the target NF/CoNi-MOF.
The self-grown MOF layer on the foamed nickel prepared in embodiment 1 is thin, as shown in SEM in fig. 2c and d, uniform array-like nanosheets are formed, and the surface is porous after annealing, which is beneficial to accelerating the charge transfer rate and improving the specific capacity thereof.
Example 2:
the method comprises the following steps: 40mg of nickel acetate and 80mg of cobalt acetate were dissolved in 30ml of deionized water, 80mg of 2, 6-naphthalenedicarboxylic acid dipotassium salt was dissolved in 30ml of water, and the solution was added dropwise to form a uniform solution, followed by stirring for 5 minutes.
Step two: and (3) placing 4 pieces of foamed nickel (which is washed and ultrasonically by acetone, deionized water, hydrochloric acid and ethanol in sequence) with the density of 1cmx1cm in the mixed solution in the step one, and transferring the mixed solution into a 60 ℃ oven to react for 48 hours to obtain the target NF/CoNi-MOF.
The thickness of the nano-sheet prepared in the embodiment 2 reaches 300nm, the loading amount of each foamed nickel sheet exceeds 3mg, as shown in SEM in figures 2e and f, the thickness of the nano-sheet layer is too thick, so that the nano-sheet layer is not beneficial to rapid conduction of charges and ions, and the interior of the nano-sheet layer is difficult to contact with electrolyte to completely participate in the reaction.
Example 3:
the method comprises the following steps: 40mg of nickel acetate and 80mg of cobalt acetate were dissolved in 30ml of deionized water, 80mg of 2, 6-naphthalenedicarboxylic acid dipotassium salt was dissolved in 30ml of water, and the solution was added dropwise to form a uniform solution, followed by stirring for 5 minutes.
Step two: and (3) placing 4 pieces of 1cm x1cm foamed nickel (sequentially washed and ultrasonically by acetone, deionized water, hydrochloric acid and ethanol) into the mixed solution in the step one, and reacting at 25 ℃ for 20 hours to obtain the target NF/CoNi-MOF.
The sample prepared in embodiment 3 is not a uniformly arrayed sheet layer, but a plurality of thick irregular sheet layers, mainly because the self-growing MOFs on the foamed nickel at 25 ℃ at normal temperature grow mainly in a stacking manner, rather than growing regularly in order, resulting in thicker and disordered MOF sheets.
Example 4:
the method comprises the following steps: 40mg of nickel acetate and 80mg of cobalt acetate were dissolved in 30ml of deionized water, 80mg of 2, 6-naphthalenedicarboxylic acid dipotassium salt was dissolved in 30ml of water, and the solution was added dropwise to form a uniform solution, followed by stirring for 5 minutes.
Step two: and (3) placing 4 pieces of 1cm x1cm foamed nickel (sequentially washed and ultrasonically by acetone, deionized water, hydrochloric acid and ethanol) into the mixed solution in the step one, and transferring the mixed solution into a 60 ℃ oven to react for 20 hours.
Step three: taking out the foamed nickel, washing, drying and placing in a muffle furnace for annealing at 350 ℃ for 2 h.
Step four: preparing 0.2mol/L of Na2Transferring 35ml of S solution and the foamed nickel in the third step into a 50ml reaction kettle, performing hydrothermal reaction in an oven at 90 ℃ for 24 hours, washing and drying to obtain the target array NiCo2S4Nanosheets.
The self-grown MOF prepared by the embodiment 4 has thinner sheet layers, the appearance is almost kept unchanged after annealing and vulcanization, as shown in SEM in figure 3, uniform array-shaped nanosheets are formed, and along with the overflow of elements such as H, O in a gas form, the surface is porous, so that the specific surface area of the material is greatly improved, as shown in TEM in figure 4. As shown in FIG. 5, the three-electrode test has good rate performance, and as shown in FIG. 6, after the hybrid supercapacitor is assembled, the hybrid supercapacitor has very stable cycle performance, and the capacity is maintained at 94.5% after 10000 cycles of cycle.
Example 5:
the method comprises the following steps: 40mg of nickel acetate and 40mg of cobalt acetate were dissolved in 30ml of deionized water, 80mg of 2, 6-naphthalenedicarboxylic acid dipotassium salt was dissolved in 30ml of water, and the solution was added dropwise to form a uniform solution, followed by stirring for 5 minutes.
Step two: and (3) placing 4 pieces of 1cm x1cm foamed nickel (sequentially washed and ultrasonically by acetone, deionized water, hydrochloric acid and ethanol) into the mixed solution in the step one, and transferring the mixed solution into a 60 ℃ oven to react for 20 hours.
Step three: taking out the foamed nickel, washing, drying and placing in a muffle furnace for annealing at 350 ℃ for 2 h.
Step four: preparing 0.2mol/L of Na2Transferring 35ml of S solution and the foamed nickel in the third step into a 50ml reaction kettle, performing hydrothermal reaction in an oven at 90 ℃ for 24 hours, washing and drying to obtain the target array NiCo2S4Nanosheets.
The sample prepared in embodiment 5 is an array-shaped cobalt-nickel sulfide nanosheet, the precursor ratio of cobalt salt and nickel salt can influence the formation of a spinel structure, a bimetallic sulfide can be obtained after 1:1 annealing and vulcanization, and NiCo can be obtained at 1:22S4。
Although the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the technical scope of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. A preparation method of self-growing bimetallic MOF on foamed nickel is characterized by comprising the following steps:
step 1: slowly adding a 2, 6-naphthalenedicarboxylic acid dimethyl salt solution into a mixed solution of cobalt acetate and nickel acetate;
step 2: and (3) transferring the clean foamed nickel into the solution in the step (1), and standing for a period of time at the temperature of 25-80 ℃ to obtain the self-growing bimetallic MOF on the foamed nickel.
2. The method according to claim 1, wherein the mass ratio of cobalt acetate, nickel acetate and the dimethyl salt of 2, 6-naphthalenedicarboxylic acid is 1-2: 1: 2.
3. The method of claim 1, wherein the nickel foam has a size of 1cmx1cm, and the clean nickel foam is obtained by ultrasonic cleaning using acetone, deionized water, hydrochloric acid, and ethanol in this order.
4. The method of claim 1, wherein the standing is at 25-80 ℃ for 10-48 hours.
5. Self-growing bimetallic MOFs on foamed nickel prepared by the method of any one of claims 1-4.
6. A preparation method of an electrode material for self-growing bimetallic MOF derivatives on foamed nickel is characterized by comprising the following steps:
step a: annealing a self-growing bimetallic MOF on a foamed nickel prepared according to any one of claims 1 to 4;
step b: carrying out hydrothermal reaction on the annealed foam nickel and sodium sulfide solution at the temperature of 90-120 ℃ for a period of time, washing and drying to obtain the electrode material, namely the arrayed NiCo2S4Nanosheets.
7. The method of claim 6, wherein in step a, the annealing temperature is 350 ± 10 ℃ and the annealing time is 2 h.
8. The method of claim 6, wherein in step b, the concentration of the sodium sulfide solution is 0.2 to 0.4 mol/L.
9. The process according to claim 6, wherein in step b, the hydrothermal reaction is carried out at 90-120 ℃ for 12-24 h.
10. A bimetallic MOF derivative electrode material self-grown on foamed nickel prepared by the method of any one of claims 6 to 9.
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| CN112337485A (en) * | 2020-11-12 | 2021-02-09 | 中国矿业大学 | Dicobalt tetrasulfide-diindium tetrasulfide compound, preparation method and application |
| CN112619610A (en) * | 2020-12-01 | 2021-04-09 | 上海交通大学 | MOFs self-growth coating metal-based dehumidifying fin and preparation method and application thereof |
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| CN112619610A (en) * | 2020-12-01 | 2021-04-09 | 上海交通大学 | MOFs self-growth coating metal-based dehumidifying fin and preparation method and application thereof |
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